Color stable compositions containing arylate-comprising polymers

ABSTRACT

The color stability of thermoplastic polymers comprising structural units derived from at least one 1,3-dihydroxybenzene and at least one organodicarboxylic acid is enhanced by combination with at least one photobleachable 4-aminocinnamic compound such as 4-dimethylaminocinnamaldehyde. The latter absorbs radiation in the range between about 360 nanometers and about 390 nanometers, balancing the radiation absorbed by hydroxybenzophenone moieties formed in the polymer.

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application is a continuation-in-part of copending U.S.application Ser. No. 09/710,005, filed Nov. 13, 2000, which is aDivision of copending U.S. application Ser. No. 09/394,211, filed Sep.10, 1999, which is incorporated herein by reference.

BACKGROUND OF THE INVENTION

[0002] This invention relates to color stability, and more particularlyto improvement of the color stability of compositions containingarylate-comprising polymers.

[0003] Photoyellowing of polymers over time is a known phenomenon whichis undesirable for aesthetic reasons. It is generally the result ofabsorption of ultraviolet (UV) radiation by the polymer, said radiationcausing photochemical reactions which typically form yellow materials.Such base polymers as polycarbonates are particularly sensitive tophotoyellowing. This can severely impede the fabrication oflight-colored articles such as white or blue articles, since theyellowing tendency can obliterate the white or blue coloring with thepassage of time. Alternatively, a higher proportion of the desiredcolorant can be introduced during fabrication but there will still be achange in appearance over time.

[0004] A recent development which can minimize photoyellowing is the useof a polymer comprising arylate structural units, for example one withstructural units derived from resorcinol and a mixture of isophthalicand terephthalic acids, which may be blended with a base polymer, mayform a copolymer therewith or may constitute a separate, external layerthereover. Such polyarylates undergo a Fries rearrangement to formhydroxybenzophenone moieties, which serve as ultraviolet absorbers andprotect the base polymer from photoyellowing.

[0005] However, the polyarylates themselves may develop a yellow colorwith the passage of time, dissipating to at least some extent thebenefits of UV absorption. This is because, while they absorb primarilyin the range between about 360 nanometers and about 390 nanometers (nm)in the near ultraviolet portion of the spectrum, their absorptionextends a small distance into the visible area, resulting in the yellowcolor development.

[0006] One known method of compensating for color development is tointroduce into the polymer a photobleachable compound which absorbs inthe same region of the spectrum as the hydroxybenzophenone moieties.Yellow dyes generally absorb in this range. Such a dye, ifphotobleachable, turns colorless at approximately the same rate as thatof photoyellowing and the overall color of the polymer remains fairlyconstant. This method is disclosed in various patents, of which examplesin the polyphenylene ether art include U.S. Pat. Nos. 4,493,915 and5,478,878.

[0007] However, the absorption of most photobleachable yellow dyescontinues into the range between about 400 nanometers and about 450nanometers in the visible region of the spectrum, farther than that ofthe hydroxybenzophenone moieties. This means that their presenceinitially introduces a yellow tinge of greater intensity than thatproduced as hydroxybenzophenone moieties are formed. Under suchconditions it is at best difficult, and at worst impossible, to producelight colored articles with consistent coloration over the passage oftime. New methods for color suppression continue to be sought in theart.

SUMMARY OF THE INVENTION

[0008] The present invention is based on the discovery that colordevelopment as the result of the formation of hydroxybenzophenonemoieties in arylate-comprising polymers can be suppressed by theaddition of photobleachable compounds having absorption limited, withinthe near ultraviolet and visible portions of the spectrum, to theaforementioned region of between about 360 nm and about 390 nm. It hasfurther been discovered that aminocinnamic compounds have suchabsorption properties.

[0009] Accordingly, in one embodiment the invention is a resinouscomposition comprising the following:

[0010] (A) at least one thermoplastic polymer comprising structuralunits derived from at least one 1,3-dihydroxybenzene and at least oneorganodicarboxylic acid, and

[0011] (B) at least one 4-aminocinnamic compound of the formula

[0012] wherein:

[0013] each of R¹ and R² is an alkyl radical, or R¹ and R² together withthe nitrogen atom separating them form a heterocyclic radical;

[0014] R³is COOR⁴, C(O)R⁴, or CN;

[0015] R⁴ is hydrogen, alkyl or aryl; and

[0016] each of R⁵ and R⁶ is hydrogen, alkyl, or aryl; or R⁵ and R⁶together with the carbon atoms connecting them form an alicyclicradical;

[0017] said 4-aminocinnamic compound absorbing radiation in the rangebetween about 360 nanometers and about 390 nanometers.

[0018] In another embodiment the invention is a resinous compositioncomprising the following:

[0019] (A) at least one thermoplastic polymer comprising structuralunits derived from at least one 1,3-dihydroxybenzene and at least oneorganodicarboxylic acid, and

[0020] (B) at least one 4-aminocinnamic compound of the formula

[0021] wherein:

[0022] each of R¹ and R² is an alkyl radical, or R¹ and R² together withthe nitrogen atom separating them form a heterocyclic radical;

[0023] R³ is COOR⁴, C(O)R⁴, or CN;

[0024] R⁴is hydrogen, alkyl or aryl;

[0025] R⁵ is hydrogen, alkyl, or aryl; and

[0026] each of R⁷ and R⁸ is hydrogen or an alkyl radical, or R⁷ and R⁸together form an alicyclic radical;

[0027] said 4-aminocinnamic compound absorbing radiation in the rangebetween about 360 nanometers and about 390 nanometers.

[0028] In another embodiment the invention is a resinous compositioncomprising the following and any reaction products thereof:

[0029] (A) at least one thermoplastic polymer comprising structuralunits derived from at least one 1,3-dihydroxybenzene and at least oneorganodicarboxylic acid, and

[0030] (B) at least one 4-aminocinnamic compound of the formula

[0031] wherein:

[0032] each of R¹ and R² is an alkyl radical, or R¹ and R² together withthe nitrogen atom separating them form a heterocyclic radical;

[0033] each of R⁵ and R⁶ is hydrogen, alkyl, or aryl; or R⁵ andR⁶together with the carbon atoms connecting them form an alicyclicradical; and

[0034] each of R⁷ and R⁸ is hydrogen or an alkyl radical, or R⁷ and R⁸together form an alicyclic radical;

[0035] said 4-aminocinnamic compound absorbing radiation in the rangebetween about 360 nanometers and about 390 nanometers.

DETAILED DESCRIPTION; PREFERRED EMBODIMENTS

[0036] For the sake of brevity, the constituents of the compositions ofthis invention are defined as “components” irrespective of whether areaction between said constituents occurs at any time. Thus, thecompositions may include said components and any reaction productsthereof. As used herein the term polymer comprises homopolymers,copolymers, interpolymers, higher order copolymers, and higher orderinterpolymers, but is not limited to these specific genera of polymericmaterials.

[0037] Component A in the compositions of the invention is athermoplastic polymer comprising structural units derived from at leastone 1,3-dihydroxybenzene and at least one organodicarboxylic acid.Suitable polymers for this purpose, specifically arylate-comprisingpolymers, are disclosed for example in commonly owned U.S. Pat. No.5,916,997, the disclosure of which is incorporated by reference herein.Arylate-comprising polymers having a glass transition temperature of atleast about 80° C. and no crystalline melting temperature, i.e., thosethat are amorphous, are preferred.

[0038] In one embodiment the polymer comprising a polyarylate is onewith structural units derived from a 1,3-dihydroxybenzene and eitherisophthalic acid or terephthalic acid or a mixture thereof comprisingstructural units of the formula

[0039] wherein each R⁹ is a substituent, especially halo or C₁₋₁₂ alkyl,and p is 0-3, optionally in combination with structural units of theformula

[0040] wherein R⁹ and p are as previously defined and R¹⁰ is a divalentC₃₋₂₂ aliphatic, alicyclic or mixed aliphatic-alicyclic radical.Moieties represented by R¹⁰ are often referred to as “soft block” units.

[0041] It is within the scope of the invention for other acid groups,such as those derived from aliphatic dicarboxylic acids such as succinicacid, adipic acid or cyclohexane-1,4-dicarboxylic acid, or from otheraromatic dicarboxylic acids such as 2,6-naphthalenedicarboxylic acid, tobe present, preferably in amounts no greater than about 30 mole percent.Most typically, however, component A may consist of units of formula IV,optionally in combination with units of formula V.

[0042] The units of formula IV contain a resorcinol or substitutedresorcinol moiety in which any R⁹ groups are preferably C₁₋₄ alkyl;i.e., methyl, ethyl, propyl or butyl. They are preferably primary orsecondary groups, with methyl being more preferred. The most preferredmoieties are resorcinol moieties, in which p is zero, although moietiesin which p is 1 are also excellent with respect to the invention.

[0043] Said 1,3-dihydroxybenzene moieties are bound to one or more typesof organodicarboxylic acid moieties, typically aromaticorganodicarboxylic acid moieties which may be monocyclic, e.g.,isophthalate or terephthalate, or polycyclic, e.g.,naphthalenedicarboxylate. Preferably, the aromatic dicarboxylic acidmoieties are isophthalate or terephthalate or a mixture thereof. Eitheror both of said moieties may be present. For the most part, both arepresent in a molar ratio of isophthalate to terephthalate in the rangeof between about 0.25:1 and about 4.0:1, preferably in the range ofbetween about 0.4:1 and about 2.5:1, more preferably in the range ofbetween about 0.67:1 and about 1.5:1, and most preferably in the rangeof between about 0.9:1 and about 1.1:1.

[0044] In the optional soft block units of formula V, resorcinol orsubstituted resorcinol moieties are again present in ester-formingcombination with R¹⁰ which is a divalent C₃₋₂₂ aliphatic, alicyclic ormixed aliphatic-alicyclic radical. Preferably, R¹⁰ is a C₃₋₂₂ straightchain alkylene, C₃₋₁₂ branched alkylene, or C₄₋₁₂ cyclo- orbicycloalkylene group. More preferably, R¹⁰ is aliphatic and especiallyC₈₋₁₂ straight chain aliphatic.

[0045] It is usually found that the arylate-comprising polymers mosteasily prepared, especially by interfacial methods, consist of units offormula IV and especially structural units derived from resorcinol incombination with structural units derived from isophthalic acid andterephthalic acid units (sometimes referred to herein as resorcinolisophthalate/terephthalate) in a molar ratio in the range of betweenabout 0.25:1 and about 4.0:1, preferably in the range of between about0.4:1 and about 2.5:1, more preferably in the range of between about0.67:1 and about 1.5:1, and most preferably in the range of betweenabout 0.9:1 and about 1.1:1. When that is the case, the presence of softblock units of formula V is usually unnecessary. If the ratio of unitsof formula IV is outside this range, and especially when they areexclusively iso- or terephthalate, the presence of soft block units maybe preferred to facilitate interfacial preparation. A particularlypreferred arylate-comprising polymer containing soft block units is oneconsisting essentially of resorcinol isophthalate and resorcinolsebacate units in a molar ratio in the range of between about 8.5:1.5and about 9.5:0.5.

[0046] Arylate-comprising polymers useful as component A may be preparedby conventional esterification reactions which may be conductedinterfacially, in solution, in the melt or under solid state conditions,all of which are known in the art. Typical interfacial preparationconditions are described for example in commonly owned U.S. Pat. No.5,916,997, the disclosure of which is incorporated by reference herein.

[0047] Also useful as component A are the block copolyestercarbonatesdisclosed and claimed in copending, commonly owned applications Ser. No.09/368,706 and Ser. No. 09/416,529, the disclosures of which are alsoincorporated by reference herein. They include block copolymerscomprising polyarylate structural units derived from a1,3-dihydroxybenzene and either isophthalic acid or terephthalic acid ora mixture thereof in combination with carbonate structural units andhaving the formula

[0048] wherein R⁹ and p are as previously defined, each R¹¹ isindependently a divalent organic radical, m is at least 1 and n is atleast about 4. Preferably n is at least about 10, more preferably atleast about 20 and most preferably about 30-150. Preferably m is atleast about 3, more preferably at least about 10 and most preferablyabout 20-200. In especially preferred embodiments m is between about 20and 50.

[0049] The arylate blocks contain structural units comprising1,3-dihydroxybenzene moieties which may be unsubstituted or substituted.Alkyl substituents, if present, are preferably straight-chain orbranched alkyl groups, and are most often located in the ortho positionto both oxygen atoms although other ring locations are contemplated.Suitable C₁₋₁₂ alkyl groups include methyl, ethyl, n-propyl, isopropyl,butyl, iso-butyl, t-butyl, nonyl, decyl, and aryl-substituted alkyl,including benzyl, with methyl being particularly preferred. Suitablehalogen substituents are bromo, chloro, and fluoro. 1,3-Dihydroxybenzenemoieties containing a mixture of alkyl and halogen substituents are alsosuitable. The value for p may be 0-3, preferably 0-2, and morepreferably 0-1. A preferred 1,3-dihydroxybenzene moiety is2-methylresorcinol. The most preferred 1,3-dihydroxybenzene moiety isunsubstituted resorcinol in which p is zero. Polymers containingmixtures of 1,3-dihydroxybenzene moieties, such as a mixture ofunsubstituted resorcinol with 2-methylresorcinol are also contemplated.

[0050] In the arylate structural units said 1,3-dihydroxybenzenemoieties are bound to aromatic dicarboxylic acid moieties which may bemonocyclic moieties, such as isophthalate or terephthalate or theirchlorine-substituted derivatives; or polycyclic moieties, such asbiphenyl dicarboxylate, diphenylether dicarboxylate, diphenylsulfonedicarboxylate, diphenylketone dicarboxylate, diphenylsulfidedicarboxylate, or naphthalenedicarboxylate, preferablynaphthalene-2,6-dicarboxylate; or mixtures of monocyclic and/orpolycyclic aromatic dicarboxylates. Preferably, the aromaticdicarboxylic acid moieties are isophthalate and/or terephthalate. Eitheror both of said moieties may be present. For the most part, both arepresent in a molar ratio of isophthalate to terephthalate in the rangeof between about 0.25:1 and about 4.0:1. When the isophthalate toterephthalate ratio is greater than about 4.0:1, then unacceptablelevels of cyclic oligomer may form. When the isophthalate toterephthalate ratio is less than about 0.25:1, then unacceptable levelsof insoluble polymer may form. Preferably the molar ratio ofisophthalate to terephthalate is in a range of between about 0.4:1 andabout 2.5:1, and more preferably in a range between about 0.67:1 andabout 1.5:1. m is at least about 10 and n is at least about 4. Softblock moieties corresponding to formula V may also be present.

[0051] In the organic carbonate blocks, each R¹¹ is independently adivalent organic radical. Preferably, said radical comprises at leastone dihydroxy-substituted aromatic hydrocarbon, and at least about 60percent of the total number of R¹¹ groups in the polymer are aromaticorganic radicals and the balance thereof are aliphatic, alicyclic, oraromatic radicals. Suitable R¹¹ radicals include m-phenylene,p-phenylene, 4,4′-biphenylene, 4,4′-bi(3,5-dimethyl)-phenylene,2,2-bis(4-phenylene)propane,6,6′-(3,3,3′,3′-tetramethyl-1,1′-spirobi[1H-indan]) and similar radicalssuch as those which correspond to the dihydroxy-substituted aromatichydrocarbons disclosed by name or formula (generic or specific) in U.S.Pat. No. 4,217,438, which is incorporated herein by reference. Aparticularly preferred divalent organic radical is2,2-bis(p-phenylene)isopropylidene and the dihydroxy-substitutedaromatic hydrocarbon corresponding thereto is commonly known asbisphenol A.

[0052] It is believed that the arylate-comprising polymers of componentA undergo thermally or photochemically induced Fries rearrangement ofarylate blocks to yield o-hydroxybenzophenone moieties or analogsthereof which serve as stabilizers to UV radiation. More particularly,at least a portion of arylate chain members can rearrange to yield chainmembers with at least one hydroxy group ortho to at least one ketonegroup. Such rearranged chain members are typicallyo-hydroxybenzophenone-type chain members and typically comprise one ormore of the following structural moieties:

[0053] wherein R⁹ and p are as previously defined. Thus, in one of itsembodiments compositions of the present invention comprisearylate-comprising polymers, at least a portion of which structuralunits have undergone Fries rearrangement. Fries rearrangement typicallygives polymer with structural units represented by a combination ofFormulas X and XI,

[0054] wherein R⁹ and p are as previously defined and wherein the molarratio of structural units represented by Formula X to structural unitsrepresented by Formula XI is in the range of between about 99:1 andabout 1:1, and preferably in the range of between about 99:1 and about80:20. Although iso- and terephthalate units are illustrated in FormulasX and XI, the dicarboxylic acid residues in the arylate residues may bederived from any suitable dicarboxylic acid residue, as definedhereinabove, or mixture of suitable dicarboxylic acid residues. Inpreferred embodiments p in both Formulas X and XI is zero and thearylate blocks comprise dicarboxylic acid residues derived from amixture of iso- and terephthalic acid residues. It is also contemplatedto introduce moieties of the types illustrated in Formulas VII, VIII,and IX via synthesis and polymerization of appropriate monomers inarylate-comprising polymers.

[0055] In a further embodiment the present invention comprisescompositions containing copolyestercarbonates containing structuralunits comprising those shown in Formula XII wherein R⁹, R¹¹, p, m, and nare as previously defined:

[0056] Component B is at least one 4-aminocinnamic compound of formulaI, II, or III. In said compounds, R¹ and R² may each be alkyl or may,together with the connecting nitrogen atom, be a heterocyclic radicalsuch as pyrrolyl or piperidinyl. Most often, each of R¹ and R² is C₁₋₄alkyl, especially methyl.

[0057] In said compounds the R³ radical, when present, may be COOR⁴,C(O)R⁴, or, CN. Preferably R³ is C(O)R⁴. R⁴ may be hydrogen, alkyl, arylor substituted aryl. Most often, R⁴ is hydrogen or C₁₋₄ alkyl.

[0058] In said compounds each of R⁵ and R⁶, when present, may be one ofthe designated radicals. Most often, each of R⁵ and R⁶ is hydrogen. Itshould also be noted that, although the configuration of formula I mightsuggest that R⁵ and R⁶ are in the trans configuration, the use of bothcis and trans compounds is within the scope of the invention.

[0059] In said compounds each of R⁷ and R⁸, when present, mayindependently be hydrogen or an alkyl radical. Alkyl radicals aretypically C₁₋₄, straight- or branched-chain, and preferably methyl.Alternatively, R⁷ and R⁸ may be joined together to form an alicyclicradical, preferably a five-membered or six-membered ring. Most often,each of R⁷ and R⁸, when present, is hydrogen.

[0060] Numerous compounds of formulas I, II, and m are available or canbe prepared by the methods described in the literature. For example,compounds of formula I may be prepared by the reaction of a suitableaminobenzaldehyde with a suitable methyl ketone.

[0061] A feature of component B is its capability of absorbing radiationin the range between about 360 nanometers and about 390 nanometers. Infact, the compounds of formula I have an absorption maximum in thisrange but do not absorb a substantial proportion of radiation in thelowest region of the visible spectrum; i.e., in the range between about400 nanometers and about 410 nanometers. Thus, it does not initiallyimpart a yellow color to the resinous composition but does, in largepart, match the absorption of the hydroxybenzophenone moieties formed inthe polyarylate.

[0062] As a result, the resinous composition has a high degree of colorstability. Moreover, the color properties of any specific compositioncan be adjusted as necessary, in both wavelength and intensity, bysuitable variations in the substituent values on the compounds offormula I, II, or III.

[0063] Component B is present in the compositions of the invention in anamount effective to balance color development as a result of theformation of hydroxybenzophenone moieties. In general, this amount willbe in the range of between about 50 ppm and about 1,000 ppm by weightbased on component A. The exact amount will depend on such factors asthe specific resin composition employed and can be readily determinedwithout undue experimentation.

[0064] The formation of the compositions of the invention may beeffected by art-recognized blending techniques. These include meltblending and solution blending.

[0065] The compositions of the invention may be employed for thefabrication of resinous articles having a high degree of lightstability. They may also be employed as weatherability improvingadditives in blends with at least one other polymer, illustrativeexamples of which include polycarbonates, polyesters, polyetherimides,polyphenylene ethers and addition polymers. Related blends are disclosedin commonly owned U.S. Pat. No. 6,143,839, the disclosure of which isincorporated by reference herein.

[0066] In another embodiment the present invention comprises multilayerarticles comprising at least two layers. In one embodiment multilayerarticles of the invention are those comprising a substrate layercomprising at least one thermoplastic polymer, thermoset polymer,cellulosic material, glass, ceramic, or metal, and at least one coatinglayer or film thereon, said coating layer or film comprising thecomposition of the invention, i.e. components A and B. Optionally, themultilayer articles may further comprise an interlayer, for example anadhesive interlayer (sometimes known as a tielayer), between anysubstrate layer and any polymer coating layer. Within the presentcontext a multilayer article is one which contains two or more layers.Multilayer articles of the invention include, but are not limited to,those which comprise a substrate layer and a coating layer of thecomposition of the invention; those which comprise a substrate layerwith a coating layer of the composition of the invention on each side ofsaid substrate layer; and those which comprise a substrate layer and atleast one coating layer of the composition of the invention with atleast one interlayer between a substrate layer and a coating layer. Anyinterlayer may be transparent, translucent, or opaque, and/or maycontain an additive, for example a colorant or decorative material suchas metal flake. If desired, an overlayer may be included over thecoating layer of the composition of the invention, for example toprovide abrasion or scratch resistance. The substrate layer, coatinglayer of the composition of the invention, and any interlayers orovercoating layers are preferably in contiguous superposed contact withone another.

[0067] Within the context of the present invention it should beunderstood that any coating layer comprising a the composition of theinvention comprising resorcinol arylate polyester chain members willalso include polymer comprising o-hydroxybenzophenone or analogous chainmembers resulting from Fries rearrangement of said resorcinol arylatechain members, for example after exposure of said coating layer toUV-light. Typically, a preponderance of polymer comprisingo-hydroxybenzophenone or analogous chain members will be on that side orsides of said coating layer exposed to UV-light and will overlay in acontiguous superposed layer or layers that polymer comprisingunrearranged resorcinol arylate chain members. If it is worn away orotherwise removed, polymer comprising o-hydroxybenzophenone or analogouschain members is capable of regenerating or renewing itself from theresorcinol arylate-containing layer or layers, thus providing continuousprotection for any UV-light sensitive layers.

[0068] The multilayer articles typically have outstanding initial gloss,improved initial color, weatherability, impact strength, and resistanceto organic solvents encountered in their final applications. Saidarticles may also be recyclable by reason of the compatibility of thediscrete layers therein.

[0069] The material of the substrate layer in the articles of thisinvention may be at least one thermoplastic polymer, whether addition orcondensation prepared. Condensation polymers include, but are notlimited to, polycarbonates, particularly aromatic polycarbonates,polyphenylene ethers, polyetherimides, polyetherketones,polyetheretherketones, polyesters and polyestercarbonates (differentfrom those that may be employed for the coating layer, as definedhereinafter), and polyamides. Polycarbonates and polyesters arefrequently preferred.

[0070] Suitable polycarbonates include homopolycarbonates comprisingstructural units of the type described for the organic carbonate blocksin the copolyestercarbonates of the invention. The most preferredpolycarbonates are bisphenol A homo- and copolycarbonates. Preferably,the weight average molecular weight of the initial polycarbonate is inthe range of between about 5,000 and about 100,000; more preferably, inthe range of between about 25,000 and about 65,000.

[0071] The polycarbonate substrate may also be a copolyestercarbonate(different from that copolyestercarbonate employed for the coating layeras defined hereinafter). Such copolymers typically comprise, in additionto the organic carbonate units, ester units such as isophthalate and/orterephthalate. Copolyestercarbonates which find use in the instantinvention and the methods for their preparation are well known in theart as disclosed in, for example, U.S. Pat. Nos. 3,030,331; 3,169,121;3,207,814; 4,194,038; 4,156,069; 4,238,596; 4,238,597; 4,487,896; and4,506,065.

[0072] Polyester substrates include, but are not limited to,poly(ethylene terephthalate), poly(1,4-butylene terephthalate),poly(trimethylene terephthalate), poly(ethylene naphthalate),poly(butylene naphthalate), poly(cyclohexanedimethanol terephthalate),poly(cyclohexanedimethanol-co-ethylene terephthalate), andpoly(1,4-cyclohexanedimethyl-1,4-cyclohexanedicarboxylate).

[0073] Suitable addition polymer substrates include homo- andcopolymeric aliphatic olefin and functionalized olefin polymers such aspolyethylene, polypropylene, poly(vinyl chloride), poly(vinylchloride-co-vinylidene chloride), poly(vinyl fluoride), poly(vinylidenefluoride), poly(vinyl acetate), poly(vinyl alcohol), poly(vinylbutyral), poly(acrylonitrile), acrylic polymers such as those of(meth)acrylamides or of alkyl (meth)acrylates such as poly(methylmethacrylate) (“PMMA”), and polymers of alkenylaromatic compounds suchas polystyrenes, including syndiotactic polystyrene. The preferredaddition polymers for many purposes are polystyrenes and especially theso-called ABS and ASA copolymers, which may contain thermoplastic,non-elastomeric styrene-acrylonitrile side chains grafted on anelastomeric base polymer of butadiene and alkyl acrylate, respectively.

[0074] Blends of any of the foregoing types and species of polymers mayalso be employed as substrates. Typical blends include, but are notlimited to, those comprising PC/ABS, PC/ASA, PC/PBT, PC/PET,PC/polyetherimide, PC/polysulfone, polyester/polyetherimide,PMMA/acrylic rubber, polyphenylene ether-polystyrene, polyphenyleneether-polyamide or polyphenylene ether-polyester. Although the substratelayer may incorporate other thermoplastic polymers, the above-describedpolycarbonates and/or addition polymers still more preferably constitutethe major proportion thereof.

[0075] The substrate layer in the multilayer articles of this inventionmay also comprise at least one of any thermoset polymer. Suitablethermoset polymer substrates include, but are not limited to, thosederived from epoxys, cyanate esters, unsaturated polyesters,diallylphthalate, acrylics, alkyds, phenol-formaldehyde, novolacs,resoles, bismaleimides, PMR resins, melamine-formaldehyde,urea-formaldehyde, benzocyclobutanes, hydroxymethylfurans, andisocyanates. In one embodiment of the invention the thermoset polymersubstrate further comprises at least one thermoplastic polymer, such as,but not limited to, polyphenylene ether, polyphenylene sulfide,polysulfone, polyetherimide, or polyester. Said thermoplastic polymer istypically combined with thermoset monomer mixture before curing of saidthermoset. Foamed substrates are also within the scope of the invention.

[0076] In one embodiment of the invention a substrate layer (such as butnot limited to a thermoplastic or thermoset substrate layer) alsoincorporates at least one filler and/or pigment. Illustrative extendingand reinforcing fillers, and pigments include silicates, zeolites,titanium dioxide, stone powder, glass fibers or spheres, carbon fibers,carbon black, graphite, calcium carbonate, talc, mica, lithopone, zincoxide, zirconium silicate, iron oxides, diatomaceous earth, calciumcarbonate, magnesium oxide, chromic oxide, zirconium oxide, aluminumoxide, crushed quartz, calcined clay, talc, kaolin, asbestos, cellulose,wood flour, cork, cotton and synthetic textile fibers, especiallyreinforcing fillers such as glass fibers, carbon fibers, and metalfibers, as well as colorants such as metal flakes, glass flakes andbeads, ceramic particles, other polymer particles, dyes and pigmentswhich may be organic, inorganic or organometallic. In another embodimentthe invention encompasses multilayer articles comprising a filledthermoset substrate layer such as a sheet-molding compound (SMC) or bulkmolding compound (BMC).

[0077] The substrate layer may also comprise at least one cellulosicmaterial including, but not limited to, wood, paper, cardboard, fiberboard, particle board, plywood, construction paper, Kraft paper,cellulose nitrate, cellulose acetate butyrate, and likecellulosic-containing materials. The invention also encompasses blendsof at least one cellulosic material and either at least one thermosetpolymer (particularly an adhesive thermoset polymer), or at least onethermoplastic polymer (particularly a recycled thermoplastic polymer,such as PET or polycarbonate), or a mixture of at least one thermosetpolymer and at least one thermoplastic polymer.

[0078] Multilayer articles encompassed by the invention also includethose comprising at least one glass layer. Typically any glass layer isa substrate layer, although multilayer articles comprising a coatinglayer of the composition of the invention interposed between a glasslayer and a substrate layer are also contemplated. Depending upon thenature of coating and glass layers, at least one adhesive interlayer maybe beneficially employed between any glass layer and any coating layerof the composition of the invention. The adhesive interlayer may betransparent, opaque or translucent. For many applications it ispreferred that the interlayer be optically transparent in nature andgenerally have a transmission of greater than about 60% and a haze valueless than about 3% with no objectionable color.

[0079] Metal articles exposed to UV-light may exhibit tarnishing andother detrimental phenomena. In another embodiment the inventionencompasses multilayer articles comprising at least one metal layer assubstrate layer. Representative metal substrates include thosecomprising brass, aluminum, magnesium, chrome, iron, steel, copper, andother metals or alloys or articles containing them, which may requireprotection from UV-light or other weather phenomena. Depending upon thenature of coating and metal layers, at least one adhesive interlayer maybe beneficially employed between any metal layer and any coating layerof the composition of the invention.

[0080] Also present in the articles of the invention is at least onecoating layer or film comprising the composition of the invention. Moreparticularly, suitable coating layers comprise polymers comprisingstructural units derived from at least one 1,3-dihydroxybenzene and atleast one organodicarboxylic acid. Typically, suitable coating layerscomprise resorcinol arylate polyesters, copolyesters (particularly thosecontaining soft-blocks), copolyestercarbonates, and mixtures thereof.Copolyestercarbonates, when used in both substrate layer and in coatinglayer, are typically different from each other in molecular structure.For example, when the coating layer contains copolyestercarbonate withresorcinol arylate polyester blocks, then any ester blocks in asubstrate copolyestercarbonate layer will typically be derived from thesame divalent organic radical as contained in the carbonate blocks ofsaid substrate.

[0081] It is also within the scope of the invention for other polymersto be present which are miscible in at least some proportions with thepolymer coating layer comprising polymer comprising structural unitsderived from at least one 1,3-dihydroxybenzene and at least oneorganodicarboxylic acid. Ilustrative examples of at least partiallymiscible polymers include polyetherimide and polyesters such as PBT,PET, PTT, PEN, PBN, PETG, PCCD, and bisphenol A polyarylate. Preferably,a coating layer polymer consists essentially the composition of theinvention comprising polymer comprising structural units derived from atleast one 1,3-dihydroxybenzene and at least one organodicarboxylic acid.

[0082] Another aspect of the invention is a method for preparing amultilayer article which comprises applying at least one coating or filmlayer of the composition of the invention to a second layer, said secondlayer comprising at least one thermoplastic polymer, thermoset polymer,cellulosic material, glass, or metal, and said coating layer comprisingpolymer comprising structural units derived from at least one1,3-dihydroxybenzene and at least one organodicarboxylic acid.

[0083] In the method of the invention, at least one thermally stablecoating or film layer is applied to a second layer, which may be thesubstrate layer or at least one intermediate layer ultimately to bedisposed between coating and substrate layers. An intermediate layer maygenerally comprise any of the materials suitable for use as thesubstrate or coating layer, and may further contain fillers andcolorants such as described hereinabove. When necessary, it may bespecifically chosen so as to provide good adhesion between substrate andcoating layers. Colorants of the previously described types may also bepresent in the coating layer.

[0084] Application of the at least one coating layer may be performed bysolvent-casting. More preferably, application of said coating layercomprises fabrication of a separate sheet thereof followed byapplication to the second layer, or by simultaneous production of bothlayers, typically in a melt process. Thus, there may be employed suchmethods as co-injection molding, coextrusion, overmolding, blow molding,multi-shot injection molding and placement of a film of a coating layermaterial on the surface of a second layer followed by adhesion of thetwo layers, typically in an injection molding apparatus; e.g., in-molddecoration, or in a hot-press. These operations may be conducted underart-recognized conditions.

[0085] It is also within the scope of the invention to apply a structurecomprising a coating layer and a second layer to a third, substratelayer, which is generally of a thermoplastic, thermoset, or cellulosicmaterial similar or identical to that of the second layer but differentfrom that of the coating layer. This may be achieved, for example, bycharging an injection mold with a structure comprising a coating layerand a second layer and injecting the substrate sheet material behind it.By this method, in-mold decoration and the like are possible. Both sidesof the substrate layer may receive the other layers, though it isusually preferred to apply them to only one side.

[0086] The thicknesses of the various layers in multilayer articles ofthis invention are most often as follows:

[0087] substrate—at least about 125μ (microns), preferably at leastabout 250μ, more preferably at least about 400μ,

[0088] coating—in the range of between about 2μ and about 2,500μ,preferably in the range of between about 10μ and about 250μ and mostpreferably in the range of between about 50μ and about 175μ,

[0089] second material, if any—in the range of between about 2μ andabout 2,500μ, preferably in the range of between about 10μ and about250μ, and most preferably in the range of between about 50μ and about175μ,

[0090] total—at least about 125μ, preferably at least about 250μ, morepreferably at least about 400μ.

[0091] The articles of this invention are characterized by the usualbeneficial properties of the substrate layer, in addition toweatherability as evidenced by improved resistance to ultravioletradiation and maintenance of gloss, and solvent resistance. Dependingupon the coating layer/substrate combination, the multilayer articlesmay possess recycling capability, which makes it possible to employ theregrind material as a substrate for further production of articles ofthe invention.

[0092] Representative multilayer articles which can be made whichcomprise the composition of the invention include aircraft, automotive,truck, military vehicle (including automotive, aircraft, and water-bornevehicles), and motorcycle exterior and interior components, includingpanels, quarter panels, rocker panels, trim, fenders, doors, decklids,trunklids, hoods, bonnets, roofs, bumpers, fascia, grilles, mirrorhousings, pillar appliques, cladding, body side moldings, wheel covers,hubcaps, door handles, spoilers, window frames, headlamp bezels,headlamps, tail lamps, tail lamp housings, tail lamp bezels, licenseplate enclosures, roof racks, and running boards; enclosures, housings,panels, and parts for outdoor vehicles and devices; enclosures forelectrical and telecommunication devices; outdoor furniture; boats andmarine equipment, including trim, enclosures, and housings; outboardmotor housings; depth finder housings, personal water-craft; jet-skis;pools; spas; hot-tubs; steps; step coverings; building and constructionapplications such as glazing, roofs, windows, floors, decorative windowfurnishings or treatments; treated glass covers for pictures, paintings,posters, and like display items; optical lenses; ophthalmic lenses;corrective ophthalmic lenses; implantable ophthalmic lenses; wallpanels, and doors; protected graphics; outdoor and indoor signs;enclosures, housings, panels, and parts for automatic teller machines(ATM); enclosures, housings, panels, and parts for lawn and gardentractors, lawn mowers, and tools, including lawn and garden tools;window and door trim; sports equipment and toys; enclosures, housings,panels, and parts for snowmobiles; recreational vehicle panels andcomponents; playground equipment; articles made from plastic-woodcombinations; golf course markers; utility pit covers; computerhousings; desk-top computer housings; portable computer housings;lap-top computer housings; palm-held computer housings; monitorhousings; printer housings; keyboards; FAX machine housings; copierhousings; telephone housings; mobile phone housings; radio senderhousings; radio receiver housings; light fixtures; lighting appliances;network interface device housings; transformer housings; air conditionerhousings; cladding or seating for public transportation; cladding orseating for trains, subways, or buses; meter housings; antenna housings;cladding for satellite dishes; coated helmets and personal protectiveequipment; coated synthetic or natural textiles; coated photographicfilm and photographic prints; coated painted articles; coated dyedarticles; coated fluorescent articles; coated foam articles; and likeapplications. The invention further contemplates additional fabricationoperations on said articles, such as, but not limited to, molding,in-mold decoration, baking in a paint oven, lamination, and/orthermoforming.

[0093] The invention is illustrated by the following non-limitingexamples.

EXAMPLE 1

[0094] A resorcinol isophthalate/terephthalate bisphenol A carbonateblock copolyestercarbonate having a 1:1 molar ratio of carbonate toester groups and a 1:1 molar ratio of isophthalate to terephthalategroups was prepared and 2 grams (g) thereof was dissolved in 8milliliters (ml) of chloroform. 4-Dimethylaminocinnamaldehyde, 700micrograms (μg), was added to the solution. A 25.4-micron film thereofwas cast on a glass surface using a doctor blade and the solvent wasevaporated. The film was mounted in a slide holder and exposed in aCi35A weatherometer (B/B filter, 0.77 watts per square meter [W/m²]).

[0095] The color data after various periods of exposure are listed inTable I. The parameters L*, a* and b* respectively represent the lightintensity (100=white light), yellow-blue hue (positive is yellow) andred-green hue (positive is red). The parameter ΔE varies directly withthe change in color of the sample and is the square root of theexpression (L*₁- L*₀)²+(a*₁- a*₀)²+(b*₁- b₀)², where L*₁, a*₁ and b*₁are the values after exposure and L*₀, a*₀ and b*₀ the initial values.TABLE I Exposure, kJ 0 57.8 117 517 L* 94.61 95.14 94.96 94.94 a* −1.14−0.75 −0.81 −1.19 b* 2.73 2.01 1.97 2.85 ΔE — 0.97 0.90 0.35

[0096] These results show that there is little change in colorproperties of the film upon weathering.

EXAMPLE 2

[0097] A film identical to that of Example 1 was compression molded at200° C. on a white bisphenol A polycarbonate plaque and the assemblagewas exposed as in Example 1. The results are given in Table II. TABLE IIExposure, kJ 0 57.1 114.1 173.2 231.7 L* 93.67 93.93 93.96 93.94 93.89a* −3.3 −3.11  −3.17 −3.31 −3.34 b* 10.01 9.60 9.74 10.26 10.67 ΔE —0.54 0.43 0.37 0.69

[0098] For comparison, the results in Table III were obtained for acontrol in which the polyarylate film contained no4-dimethylaminocinnamaldehyde. TABLE III Exposure, kJ 0 57.4 116.7 229.7348.2 L* 94.76 94.82 94.75 94.67 94.58 a* −0.49 −2.94 −3.15 −3.45 −3.57b* 3.27 8.79 9.50 10.86 11.22 ΔE — 6.04 6.77 8.15 8.53

[0099] It can be seen that the color change for the control wassubstantially greater than that for the plaque coated with thecomposition of the invention.

EXAMPLE 3

[0100] A film is prepared and exposed in a weatherometer as described inExample 1 except that in place of 4-dimethylaminocinnamaldehyde there isemployed an equimolar amount of a compound of the formula (III):

[0101] wherein each of R¹ and R² is methyl; each of R⁵ and R⁶ ishydrogen; and each of R⁷ and R⁸ is hydrogen. The film shows littlechange in color properties upon weathering compared to a similar filmwithout the compound shown.

EXAMPLE 4

[0102] A film containing the compound of Example 3 is prepared andexposed in a weatherometer as described in Example 1 except that inplace of a resorcinol isophthalate/terephthalate bisphenol A carbonateblock copolyestercarbonate there is employed an arylate-comprisingpolymer containing soft block units consisting essentially of resorcinolisophthalate and resorcinol sebacate units in a molar ratio between8.5:1.5 and 9.5:0.5. The film shows little change in color propertiesupon weathering compared to a similar film without the compound ofExample 3.

EXAMPLE 5

[0103] A film identical to that of Example 4 is compression molded on awhite bisphenol A polycarbonate plaque and the assemblage is exposed ina weatherometer as in Example 1. For comparison, results are alsoobtained for a control film made without the compound of Example 3. Thecolor change for the control is substantially greater than that for theplaque coated with the composition of the invention.

[0104] While the invention has been illustrated and described in typicalembodiments, it is not intended to be limited to the details shown,since various modifications and substitutions can be made withoutdeparting in any way from the spirit of the present invention. As such,further modifications and equivalents of the invention herein disclosedmay occur to persons skilled in the art using no more than routineexperimentation, and all such modifications and equivalents are believedto be within the spirit and scope of the invention as defined by thefollowing claims.

What is claimed is:
 1. A resinous composition comprising the following:(A) at least one thermoplastic polymer comprising structural unitsderived from at least one 1,3-dihydroxybenzene and at least oneorganodicarboxylic acid, and (B) at least one 4-aminocinnamic compoundof the formula

wherein: each of R¹ and R² is an alkyl radical, or R¹ and R² togetherwith the nitrogen atom separating them form a heterocyclic radical; eachof R⁵ and R⁶ is hydrogen, alkyl, or aryl; or R⁵ and R⁶ together with thecarbon atoms connecting them form an alicyclic radical; and each of R⁷and R⁸ is hydrogen or an alkyl radical, or R⁷ and R⁸ together form analicyclic radical; said 4-aminocinnamic compound absorbing radiation inthe range between about 360 nanometers and about 390 nanometers.
 2. Thecomposition according to claim 1 wherein component A comprisesstructural units of the formula

wherein each R⁹ is a substituent and p is 0-3, optionally in combinationwith structural units of the formula

wherein R⁹ and p are as previously defined and R¹⁰ is a divalent C₄₋₁₂aliphatic, alicyclic or mixed aliphatic-alicyclic radical.
 3. Thecomposition according to claim 2 wherein component A consists ofstructural units of formula IV and p is zero.
 4. The compositionaccording to claim 3 wherein the structural units are mixedisophthalate/terephthalate units.
 5. The composition according to claim2 wherein component A consists of structural units of formulas IV and V,p is zero and R¹⁰ is a C₈₋₁₂ straight chain aliphatic radical.
 6. Thecomposition according to claim 5 wherein the structural units of formulaIV are mixed isophthalate/terephthalate units.
 7. The compositionaccording to claim 2 wherein component A is a block copolyestercarbonatecomprising structural units of the formula

wherein each R⁹ is a substituent, each R¹¹ is independently a divalentorganic radical, m is at least about 10, n is at least about 4 and p is0-3.
 8. The composition according to claim 7 wherein p is zero and R¹¹is 2,2-bis(p-phenylene)isopropylidene.
 9. The composition according toclaim 8 wherein the ester units are mixed isophthalate/terephthalateunits.
 10. The composition according to claim 1 wherein each of R¹ andR² is C₁₋₄ alkyl and each of R⁵, R⁶, R⁷, and R⁸ is hydrogen.
 11. Thecomposition according to claim 10 wherein each of R¹ and R² is methyl.12. The composition according to claim 10 wherein R¹ and R² takentogether are piperidinyl.
 13. The composition according to claim 1wherein component B is present in the range of between about 50 ppm andabout 1,000 ppm by weight based on component A.
 14. A resinouscomposition comprising the following: (A) at least one thermoplasticpolymer comprising structural units derived from a resorcinol and atleast one of isophthalic and terephthalic acids, and (B) an amount in arange of between about 50 ppm and about 1,000 ppm by weight, based oncomponent A, of at least one aminocinnamic compound of the formula

wherein: each of R¹ and R² is an alkyl radical, or R¹ and R² togetherwith the nitrogen atom separating them form a heterocyclic radical; eachof R⁵ and R⁶ is hydrogen, alkyl, or aryl; or R⁵ and R⁶ together with thecarbon atoms connecting them form an alicyclic radical; and each of R⁷and R⁸ is hydrogen or an alkyl radical, or R⁷ and R⁸ together form analicyclic radical; said 4-aminocinnamic compound absorbing radiation inthe range between about 360 nanometers and about 390 nanometers.
 15. Thecomposition of claim 14 in which at least a portion of thermoplasticpolymer has undergone Fries rearrangement.
 16. A resinous compositioncomprising the following: (A) at least one block copolyestercarbonatecomprising moieties of the formula

wherein R⁹ and p are as previously defined, each R¹¹ is independently adivalent organic radical, m is at least about 10 and n is at least about4. (B) an amount in a range of between about 50 ppm and about 1,000 ppmby weight, based on component A, of at least one aminocinnamic compoundof the formula

wherein: each of R¹ and R² is an alkyl radical, or R¹ and R² togetherwith the nitrogen atom separating them form a heterocyclic radical; eachof R⁵ and R⁶ is hydrogen, alkyl, or aryl; or R⁵ and R⁶ together with thecarbon atoms connecting them form an alicyclic radical; and each of R⁷and R⁸ is hydrogen or an alkyl radical, or R⁷ and R⁸ together form analicyclic radical; said 4-aminocinnamic compound absorbing radiation inthe range between about 360 nanometers and about 390 nanometers.
 17. Thecomposition of claim 16 in which at least a portion of thermoplasticpolymer has undergone Fries rearrangement.
 18. A multilayer article withat least one layer comprising the composition of claim 1 .
 19. Themultilayer article of claim 18 which is an aircraft, automotive, truck,military vehicle, military aircraft, water-borne military vehicle, ormotorcycle exterior or interior component, including a panel, quarterpanel, rocker panel, trim, fender, door, decklid, trunklid, hood,bonnet, roof, bumper, fascia, grill, mirror housing, pillar applique,cladding, body side molding, wheel cover, hubcap, door handle, spoiler,window frame, headlamp bezel, headlamp, tail lamp, tail lamp housing,tail lamp bezel, license plate enclosure, roof rack, or running board;an enclosure, housing, panel, or part for an outdoor vehicle or outdoordevice; an enclosure for an electrical or telecommunication device;outdoor furniture; an article for boat or marine equipment, includingtrim, enclosures, and housings; an outboard motor housing; a depthfinder housing; a personal water-craft; a jet-ski; a pool; a spa; ahot-tub; a step; a step covering; a building or construction applicationincluding glazing, roofs, windows, floors, decorative window furnishingsor treatments; a treated glass cover for pictures, painting, posters, ordisplay items; an optical lens; an ophthalmic lens; a correctiveophthalmic lens; an implantable ophthalmic lens; a wall panel, or door;a protected graphic; an outdoor or indoor sign; an enclosure, housing,panel, or part for automatic teller machines (ATM); an enclosure,housing, panel, or part for lawn or garden tractors, lawn mowers, ortools, including lawn and garden tools; a window or door trim; anarticle of sports equipment or a toy; an enclosure, housing, panel, orpart for a snowmobile; a recreational vehicle panel or component; anarticle of playground equipment; an article made from combinations ofplastic and wood; a golf course marker; a utility pit cover; a computerhousing; a desk-top computer housing; a portable computer housing; alap-top computer housing; a palm-held computer housing; a monitorhousing; a printer housing; a keyboard; a FAX machine housing; a copierhousing; a telephone housing; a mobile phone housing; a radio senderhousing; a radio receiver housing; a light fixture; a lightingappliance; a network interface device housing; a transformer housing; anair conditioner housing; an article of cladding or seating for publictransportation; an article of cladding or seating for trains, subways,or buses; a meter housing; an antenna housing; an article of claddingfor satellite dishes; a coated helmet or other article of personalprotective equipment; a coated synthetic or natural textile; a coatedphotographic film or photographic print; a coated painted article; acoated dyed article; a coated fluorescent article; or a coated foamarticle.
 20. A multilayer article with at least one layer comprising thecomposition of claim 14 .
 21. A multilayer article with at least onelayer comprising the composition of claim 15 .
 22. A multilayer articlewith at least one layer comprising the composition of claim 16 .
 23. Amultilayer article with at least one layer comprising the composition ofclaim 17 .
 24. A method for preparing a resinous composition comprisingthe following: (A) at least one thermoplastic polymer comprisingstructural units derived from at least one 1,3-dihydroxybenzene and atleast one organodicarboxylic acid, and (B) at least one 4-aminocinnamiccompound of the formula

wherein: each of R¹ and R² is an alkyl radical, or R¹ and R² togetherwith the nitrogen atom separating them form a heterocyclic radical; eachof R⁵ and R⁶ is hydrogen, alkyl, or aryl; or R⁵ and R⁶ together with thecarbon atoms connecting them form an alicyclic radical; and each of R⁷and R⁸ is hydrogen or an alkyl radical, or R⁷ and R⁸ together form analicyclic radical; said 4-aminocinnamic compound absorbing radiation inthe range between about 360 nanometers and about 390 nanometers, whereinthe method comprises melt blending components (A) and (B).
 25. Themethod according to claim 24 wherein component A comprises structuralunits of the formula

wherein each R⁹ is a substituent and p is 0-3, optionally in combinationwith structural units of the formula

wherein R⁹ and p are as previously defined and R¹⁰ is a divalent C₄₋₁₂aliphatic, alicyclic or mixed aliphatic-alicyclic radical.
 26. Themethod according to claim 25 wherein component A consists of structuralunits of formula IV and p is zero.
 27. The method according to claim 26wherein the structural units are mixed isophthalate/terephthalate units.28. The method according to claim 25 wherein component A consists ofstructural units of formulas IV and V, p is zero and R¹⁰ is a C₈₋₁₂straight chain aliphatic radical.
 29. The method according to claim 28wherein the structural units of formula IV are mixedisophthalate/terephthalate units.
 30. The method according to claim 25wherein component A is a block copolyestercarbonate comprisingstructural units of the formula

wherein each R⁹ is a substituent, each R¹¹ is independently a divalentorganic radical, m is at least about 10, n is at least about 4 and p is0-3.
 31. The method according to claim 30 wherein p is zero and R¹¹ is2,2-bis(p-phenylene)isopropylidene.
 32. The method according to claim 31wherein the ester units are mixed isophthalate/terephthalate units. 33.The method according to claim 24 wherein each of R¹ and R²is C₁₋₄ alkyland each of R⁵, R⁶, R⁷, and R⁸ is hydrogen.
 34. The method according toclaim 33 wherein each of R¹ and R² is methyl.
 35. The method accordingto claim 33 wherein R¹ and R² taken together are piperidinyl.
 36. Themethod according to claim 24 wherein component B is present in the rangeof between about 50 ppm and about 1,000 ppm by weight based on componentA.
 37. A method for preparing a resinous composition comprising thefollowing: (A) at least one thermoplastic polymer comprising structuralunits derived from a resorcinol and at least one of isophthalic andterephthalic acids, and (B) an amount in a range of between about 50 ppmand about 1,000 ppm by weight, based on component A, of at least oneaminocinnamic compound of the formula

wherein: each of R¹ and R² is an alkyl radical, or R¹ and R² togetherwith the nitrogen atom separating them form a heterocyclic radical; eachof R⁵ and R⁶ is hydrogen, alkyl, or aryl; or R⁵ and R⁶ together with thecarbon atoms connecting them form an alicyclic radical; and each of R⁷and R⁸ is hydrogen or an alkyl radical, or R⁷ and R⁸ together form analicyclic radical; said 4-aminocinnamic compound absorbing radiation inthe range between about 360 nanometers and about 390 nanometers, whereinthe method comprises melt blending components (A) and (B).
 38. Themethod of claim 37 in which at least a portion of thermoplastic polymerhas undergone Fries rearrangement.
 39. A resinous composition comprisingthe following: (A) at least one block copolyestercarbonate comprisingmoieties of the formula

wherein R⁹ and p are as previously defined, each R¹¹ is independently adivalent organic radical, m is at least about 10 and n is at least about4, (B) an amount in a range of between about 50 ppm and about 1,000 ppmby weight, based on component A, of at least one aminocinnamic compoundof the formula

wherein: each of R¹ and R² is an alkyl radical, or R¹ and R² togetherwith the nitrogen atom separating them form a heterocyclic radical; eachof R⁵ and R⁶ is hydrogen, alkyl, or aryl; or R⁵ and R⁶ together with thecarbon atoms connecting them form an alicyclic radical; and each of R⁷and R⁸ is hydrogen or an alkyl radical, or R⁷ and R⁸ together form analicyclic radical; said 4-aminocinnamic compound absorbing radiation inthe range between about 360 nanometers and about 390 nanometers, whereinthe method comprises melt blending components (A) and (B).
 40. Thecomposition of claim 39 in which at least a portion of thermoplasticpolymer has undergone Fries rearrangement.